THERMAL AND LASER PYROLYSIS OF HYDROCARBON ANION-RADICALS

The solid anion radical salts resulting from the reductions of naphtha lene, pyrene, perylene, benzo[k]fluoranthene, and biphenyl with lithiu m, cesium, and potassium metals were either pyrolyzed at 200-380 degre es C or irradiated with a pulsed frequency doubled Nd:YAG laser (532 n m wavelength). For both the pyrolytic and laser photolytic studies the only volatile products were hydrogen and methane. The hydrogen origin ated from the anionic polymerization of the anion radical. Evidence is presented that suggests that the methane results from a carbene inter mediate, which in turn reacts with the H-2. Consistent with the H-2 fo rmation, MALDS mass spectral analysis revealed the presence of dimers, trimers, and higher polymers of the polyaromatic hydrocarbon in the r emaining nonvolatile products. There were considerably fewer low molec ular weight oliomers produced via the laser photolysis than via the th ermolysis.